Contacting gaseous fluids and solid particles



May 2, v1950 l H. z. MARTIN coNTAcTING GAsEus FLUIDs AND'soLIn PARTICLES Original Filed Dec, 30, 1941 2 Sheets-She'et 1 Homer-ZV. martn. v 3m/enter b/ZW/WW Clbbornef May 2, 1950 H. z. MARTIN coNTAcTING GAsEoUs FLUIDs AND SOLID PARTICLES Original Filed Dec. 30, 1941 2 Sheets-Sheet 2 f b5" C'Jbbofneg Patented May 1950 UNI-rap S'IA'rlszs"PATENT oFFlcE VCONTACTING GASEOUS FLUIDS AND SOLID PARTICLES Homer z. Martin, mene, N. J., signor to suma; ard Oil Development Company, a corporation of Delaware original application December so', 1941, serian No. 424,872. .Divided and this application March 16, 1946, serial No. 654,846

, l This invention relates to catalytic reactions and more particularly relates to catalytic reactions involving the production of hydrocarbons of relatively low boiling point suitable for use as motor fuels.

According to this.invention catalyst in inely divided form is mixed with solid inert particles in finely divided form so that amixture of solid particles is obtained which when regenerated perature. Using this invention, a heating or superheating furnace such as a coil heater for vaporizing the oil feed is eliminated. Also'regen eration coolers for controlling the temperature in the regeneration zone during regeneration are eliminated and the hot regenerated solid particles are used without any intermediate cooling for mixture with the oil feed.

Several forms of the invention are shown in the drawings and will be more speciiically described in the description hereinafter.

In the drawings:

Figure l represents one form of apparatus adapted for carrying out the invention in which the regenerator is above the reactor and solid particles are withdrawn in a dense phase from the bottom portion of both the regeneratorand the reactor;

Figure 2 represents another form of lapparatus adapted for carrying out the invention in which the regenerator is supported near the.

ground and is of the upilow type, whereas the catalyst in a dense phase is removed from the bottom portion of the reactor; and

Figure.3 represents another form of apparawhich the regenerator is in an elevated position and of the bottom draw-oir type whereas the reactor is at a lower level and of the upow type.

, Referring now to the drawing and to Figure 1, the reference character 'III ldesignates a reaction zone and the reference character i2 designates a regenerator.` Solid particles including inert and catalytic particles are withdrawn from y tus adapted for carrying out the invention in 5 Claims. (CL 196-52) the regenerator I2 by means of a standpipe I4 having a suitable control valve Il for controlling the amount of solid particles directly introduced into the reaction zone III. The solid particles un dergoing regeneration in the regenerator l2 are maintained in a uidized condition and ilow therefrom through the standpipe I4 like a liquid. As will be later pointed out in greater detail, the solid inert particles act as heat carriers and are used because catalyst only in-such large amounts would render the reaction uncontrollable in cer-- tain reactions as in catalytic cracking of hydrocarbon oils..

Liquid oil feed, preferably preheated, is introduced into the bottom portion of the reaction zone Ill through line I8. The solid particles including the inert and catalyst particles are maintained in a uidized condition in the reaction zone I 0 and in this way the solid particles are maintained-in a turbulent condition and the tem- 'perature inthe reaction zone is substantially uniform. The level of the iluidized mass in the reactionzone l0 is shown at 22. The level 22 is not quiescent but is more like the surface of a violently boiling liquid. The lower end of standpipe I4 extends below the level 22 of the iiuidized mass in reaction zone l0.

As shown in the drawing, the reactionzone comprises a relatively shallow cup-shaped receptacle which is concentric with and arranged in the lower part of a larger vessel 24. The shallow receptacle is suitably supported on the b ottom of the larger vessel 24 by means diagrammatically shown at 26. As the reaction zone i0 is of a smaller diameter than the 'larger vessel 24, an annular space 28 is provided between the reaction zone lli and the larger veel 24 into which the solid particles overilow from the reaction zone l0. Suitable stripping gas is intro# duced into the solid particles in the annular space.

28 by means of line .32 to remove volatile hydrocarbons from the solid particles.

The velocity of the vapors passing through the solid particles in the reaction zone III is selected to maintain a uidized mass therein. As more oil and more solid particlesare fed into the reaction zone I0, the reaction products in vapor form pass upwardly into the enlarged space 34 in the larger vessel 24 and this enlarged space forms a settling chamber for removing solid particles from the reaction products. In addition, the uidized solid particles in relatively dense condition overow the upper rim of the reaction zone Ill and flow'into the annular space 28 where additional quantities of vaporous reaction products are released. The solid particles in the annular space are also maintained in fiuidized condition but their density is greater than the density of the fluidized mixture in the reaction zone The reaction products in vapor form pass upwardly from' the enlarged chamber 34 and preferably pass through additional separating means shown diagrammatically at 36. If desired, cyclone separators may be used. If the upper narrowed portion 31 of the larger vessel 24 is enlarged to form a settling chamber, the additional separating means shown at 36 may be eliminated. The upper narrow portion 31 is closed at its upper end by a partition plate 31'.

The vaporous reaction products leave the upper portion of the vessel 24 through line 3B and are introduced into the lower portion of a fractionating tower 40. The reaction products contain a small amount of solid particles and these solid particles are removed in the lower portion of the fractionating tower as will be hereinafter described in greater detail.

In catalytic reactions where the solid particles become contaminated or partially spent after a reaction period it is necessary to regenerate the solid particles. vFor example, in the catalytic cracking of hydrocarbons, carbonaceous material is deposited on the catalytic and solid particles and the catalytic and solid particles are regenerated by burning off the carbonaceous material. The used solid particles containing catalyst are withdrawn from theannular space 23 by means of standpipes 42 provided with control valves ed. The standpipes 42 communicate with the bottom portion of the draw-off compartment 28 and the solid particles flow from the draw-off compartment 28 into the standpipes 62. A suitable regenerating gas such as air or other oxygen-containing gas is introduced through line 46 into branch lines d8 and 52 for introducing the regenerating gas into the used catalyst and solid particles withdrawn from the annular chamber As above stated, the iiuidized solid particles act like a liquid and produce a pressure at the bottom of the standpipe d2 which is suicient to carry the solid particles tothe regeneration zone i2. By introducing a regenerating gas below the valves M, a light suspension of solid particles in a gas is formed and the pressure produced by the column of dense solid particles is suiiicient to lforce the used solid particles upwardly in the branch lines 54 and 56 for conveying the solid particles to the regeneration zone l2. In addition to this column in Figure 1, there is a pressure of about 8 pounds per square inch gauge in vessel 24 and reaction zone Ill and this pressure is added to the column to convey the solid particles to regeneration zone I2. The regeneration is under a pressure of only about 1 pound per square inch gauge. The used solid particles are introduced into the regeneration zone below a perforated distribution plate 58. The velocity of the vgas mixed with the soli particles being regenerated is so selected that the solid particles are maintained in a relatively dense fluidized condition and have a level designated at 62. The level E2 is not quiescent but resembles a violently boiling liquid. While the level 62 is shown at one position in Figure 1, it is understood Vthat this level may be varied and may be at higher or lower levels-for different reactions or for diiferent oil stocks. Above the level 62 the regeneration'zone I2 is provided with an enlarged chamber 64 which forms a settling chamber for separating solid particles from the gases of regeneration. f The gases of regeneration pass overhead from the enlarged chamber 64 through line BB and are further treated to recover residual amounts of solid particles and for preheating the liquid feed when it is a low coke-forming stock as will be presently described. When the liquid feed is of a high coke-forming stock it is preferably cooled after passing through the scrubber presently to be described.

The standpipe I4 used for conveying hot regenerated solid particles from the regeneration zone I2 to the reaction zone I0 has its upper end 68 extending above the distribution plate 58. In this way the solid particles are withdrawn from the body of the fiuidized mixture in the regeneration zone I2. The regenerated solid particles in standpipe I4 may be stripped of oxygen-containing gas by introducing a stripping gas such as steam through line 69.

The gases of regeneration passing through line 66 are passed through a suitable cooler 69' provided with vertical tubes 12. A heat exchange medium is circulated through the heat exchanger and around the tubes 12 through inlet line 14 and outlet line 16. The cooled gases of regeneration are then passed through line 18 and introduced into the bottom portion of a scrubber or scrubbing tower' 82.

Liquid feed such as liquid oil is passed through line 84 by means of pump 86 and is introduced into the upper portion of the scrubbing tower 82. The liquid feed is sprayed into the upper portion of the scrubbing tower 82 by means of a spray device 88. The falling droplets of liquid feed scrub out any entrained solid particles and at the same time the liquid feed is preheated by absorbing heat from the hot gases of regeneration. The scrubbing tower may be provided with baffles, discs and doughnuts or packing to provide a large surface for contacting the oil with the gases. The cooled and scrubbed gases of regeneration leave the top of the scrubbing tower through a valved line 92 and may be vented to the atmosphere.

The preheated liquid feed when it is of alow coke-forming type and containing the solid particles scrubbed out of the gases of regeneration is withdrawn from the bottom of the scrubbing tower 82 through line 94 and is passed to coil 96 in heat exchanger 91 by a pump 98. In the heat exchanger 91 the oil feed or liquid feed is indirectly contacted with bottoms containing solid particles scrubbed from the vaporous reaction products and withdrawn from the fractionating tower dii through line IIlZ by means of pump I04 and passed through line H36 and through the heat exchanger 91. The partly cooled bottoms are withdrawn from the heat exchanger through line H08. The preheated liquid feed leaves the heat exchanger'91 through line II2 and may be combined with at least a portion of the cooled bottoms passing through line II4 and the mixture passed through line IIS and valved by-pass line I I8 and I I8 around heat exchanger or cooler I I9 to the liquid inlet line I8 hereinbefore de- I scribed.

gl and heat exchanger or cooler I I9 to cool the feed feed stock passed through lines ||9' and H8' to line I8. The mixture of preheated liquid feed and bottoms passing through line ||6 may be A passed through valved line |25 and through the coil |26 in the heat exchanger ||9 to cool the mixture. A heat exchange medium is introduced into the heat exchanger ||9 by means of line |21 and leaves the heat exchanger through line |28. Water may be used in the heat exchanger ||9 to produce hot water and/or steam which may be used in other parts of the process. When the oil feed is to be passed through line |25, the valve in the by-pass line ||8 is closed.

'I'he vaporous reaction products introduced into the bottom portion of the fractionating tower 40 are at a relatively high temperature and in order to desuperheat them and condense higher boiling contituents and also to remove entrained solid particles, at least a portion of the bottoms is taken o' and cooled and returned to the fractionating tower 40. At least a part of the bottomswithdrawn through line |02 is passed scrubbing tower shown in Figure 1 are preferably used with the form of the invention shown in Figure 2.

The reaction zone |14'is similar to the reaction zone l described in Figure 1 and' comprises a relatively shallow cup-shaped vessel which is supported in a larger vessel |15by means of suitable supporting means diagrammatically shown at |16.

Solid particles including catalyst particles are directly introduced from hopper |82 intothe reaction zone |14 by means` of standpipe |84 having a control valve |86. The solid particles through line |32 and heat exchanger |34 wherein the bottoms are indirectly contacted with a heat exchange medium introduced through line |86 and leaving the heat exchanger |34 through line |38. Water may be used as the heat exchange medium and the steam produced may be used in other parts of the process.

The cooled bottoms are withdrawn from the heat exchanger |34 through line |42 and are passed through line |44 having a valve |46 which introduces the 'cooled bottoms into the bottom portion of the fractionating tower 40. The line |44 at its outlet end in the fractionating tower is provided with spray means |48 for spraying the cooled bottoms above a, baille means |52 whereby intimate contact is provided between the vaporous reaction products and the cooled bottoms and entrained solid particles are scrubbed out to form a slurry. A portion of the cooled bottoms from line |08 may be introduced into line |44 and returned to the bottom of the fractionatingv tower 40.

The portion of the cooled bottoms passing through line ||4 comprises a slurry and contains catalyst and s olid particles which were washed out of the vaporous reaction products and the slurry formed 'is returned to the reaction zone |0 with the oil fed through line I8.

The vaporous reaction products pass upwardly in the fractionating tower where they are fractionated by contact with downowing condensate l oil and the desired product is taken overhead in vapor form through line |54. Where relativelyy heavy hydrocarbons are cracked to form lower boiling hydrocarbons, the fraction or product taken through line |54 comprises vgases and gasoline constituents which may be further treated in any suitable or conventional manner to separate motor` fuel. In the treatment of hydrocarbons any desired side streams or fractions may be removed from the side of the fractionatare maintained,f in uidized condition in the reaction zone |14 and overow into the annular space |88 as described in connection with Figure 1 of the drawings. Stripping gas such as steam is preferably introduced intothe denser uidized mixture in the the annular chamber |88 through line |92. A

The spent catalyst or solid particles flow into the standpipe |94 provided below the larger outer vessel |15. The standpipe |94 is provided with a control valve |96 near its lower end.

The iiuidized mixture in the reaction zone |14 has a level |91 and the fluid'ized mixture in the overflow chamber |88 has a level |98. The height of fluidized mixture from the level |98 to lthe valve |96 produces -a pressure similar to hydrostatic pressure which is sufficient to forcethe spent catalyst to the regeneration zone presently to be described.

Regenerating gas such as air or oxygen-containing gas is introduced into the spent catalyst vand solid particles below the valve |96 by means of line |99 to form a relatively light suspension of solid particles in gas. The light suspension is passed through line 202 and into the bottom of 4a regeneration zone 204. The velocity of the regenerating gas is so selected that a level 205 of fluidized catalyst or solid particles undergoing regeneration is formed inthe regeneration zone 204. While'the' level 205 is shown in one position in Figure 2, it is to be understood-that it may be varied and may be higher or lower'with different oil stocks o'r different reactions. In this form of the invention it will be seen that' the regeneration zone 204 is supported near ground level and in order to move the particles to a position above the reaction zone |14 an upflow regeneration zone is use d. 'Ihat is, all of the regeneration gases and the solid particles pass overhead from the' regeneration zone 204 through line 206 and are passed into a separating zone of regeneration pass overhead through line'2l6 and in the preferred form of the invention a cooler and scrubber are used as shown in Figure l for removing entrained solid particles from the regeneration gases and also to recover heat from the regeneration gases where a low coke-forming feed stock is used.

If desired, a suitable stripping gas such as steam may be introduced into the regenerated catalyst or solid particles in hopper |82 through line-2|8.

In the reaction zone |14 the velocity of the vapors passing therethrough is selected so that a iiuidized mass oi solid particles is obtained. The vaporous reaction products leaving the reaction zone |14 enter the enlarged space or chamber 2 I9 wherein further separation of solid particles from vapors takes place. The -upper portion of the vessel |15 is shown as restricted on the drawing and is provided with additional separating means 226 thereon for separating additional quantities of solid particles from the reaction products. Instead of having the separating means 220 the upper portion of the outer vessel |15 may be enlarged to form a separating chamber or settling chamber and in this case the further separating' means 220 such as cyclone separators may be eliminated.

The vaporous reaction products leave the top of the vessel |15 through line 22| and are prefl erably passed to the bottom portion of a fractionating tower similar to that shown in Figure l of the drawings. y

In the form of the invention shown in Figure 3 ofthe drawings the regenerator is shown in an elevated position and is of the bottom draw-ofi type whereas the reactor is of the upfiow type and is arranged near the ground level. In this form of the invention the liquid feed is introduced through line 236 and is mixed with hot regenerated solid particles introduced into the mixing chamber 23| from standpipe 232 having a control valve 234. The'mixture is passed through line 236 and upwardly through a high velocity upilowreactor 238 wherein the solid particles and oil vapors are mixed' and the oil is converted to lower boiling hydrocarbons. In this type of reactor the vaporous reaction products and the solid particles pass overhead from the top of the reaction zone 238. The upper portion of the reaction zone 238 is provided with Va spiral separator 242 to give the suspension aspiral motion and to' assist in separating solid particles from vaporous reaction products.

Arranged above the top of the reaction zone 238 is an enlarged chamber 244 into which the top of the reaction zone discharges. larged area for gas ilow, the velocity of the vapors and gases is decreased and there is a separation of solid particles from vapors and gases. The solid particles are collected in an annular chamber 246 surrounding the upper portion of the reaction zone 238 and forming part ci the enlarged chamber 244 surrounding the upper portion of the reaction zone 233. The level of the separated solid particles in the annular chamber 246 is shown at 248.

The separated reaction products in vapor form pass upwardly into the restricted portion 25| of the outer vessel 244 and preferably pass through additional separating means 252 such as diagrammatically shown cyclone separators for separating additional quantities of solid particles from the vapors. Instead of restricting the upper portion of the vessel 244, the chamber may be enlarged to form an additional settling chamber and in this event the separating means such as cyclones shown diagrammatically at 252 may be omitted.

The separated vaporous reaction products leave the top of the enlarged chamber 244 through line 254 and are preferably passed to a fractionating tower similar to that shown in Figure l of the drawings.

The spent or fouled solid particles in the annular space 246 are preferably stripped to remove Due to the eny 8 volatile hydrocarbons and the like by introducing a suitable 'stripping gas such as steam through line 256. These solid particles are also maintained in a fluidized condition and flow into 'a standpipe 258 provided with a control valve 262 and then to a mixing chamber 263.y Regenerating gas is'introduced into the mixing chamber 263 by means of line 264 and the mixture of solid particles and gas is passed through line 266 and upwardly through. line 268 into the bottom portion of a regeneration zone 212. The uidized fouled solid particles are maintained in a relatively dense condition and the pressure formed by the head of iluidized solid particles extending from the level 248 to the valve 262 is sumcient to return the relatively light suspension passing through lines 266 and 268 to the regeneration zone 212.

In Figure 3 the chamber 244 is under about 8 pounds per square inch pressure whereas the regeneration zone 212 is under about-1 pound per square inch pressure. With these pressures and with the columns of uidized solid particles including standpipes 232 and 258, theflow of the streams of iluidized solid particles is as above described.

The solid particles to be regenerated are introduced into the regeneration zone 212 below the perforated distribution plate 2i4. In the regeneration zone 212 the particles are maintained in a iiuidized condition during regeneration and the mass has a level as shown at 216. As above pointed out in connection with Figures l and 2, level 216 may similarly be varied. The velocity of the regenerating gas is so selected or maintained that there is some settling of the particles and a uidized mixture is formed. The regeneration gases leaving the iluidized mixture pass upwardly into settling space 216 and then into the restricted portion 211 oi? the regeneration vessel 'and may be passed through separating means 218 diagrammatically shown for removing additional amounts of solid particles from regeneration gases. The regeneration gases leave the top of the vessel 212 through line 282 and may be passed through a cooler and scrubber as shown in Figure 1 of the drawings. Instead of having the upper portion of the vessel 212 restricted at 211 the vessel may have an enlarged dome to provide additional settling space and in this case the additional separating means 218 may be eliminated.

The regenerated solid particles are withdrawn in fluidized condition from a withdrawal `com partment 284 shown as extending above the distribution plate 214 and communicating with the standpipe 232. Preferably, a stripping gas such as steam is introduced into the withdrawal chamber 284 through line 286 to remove residual oxygen-containing gas from the hot regenerated solid particles.

To 4accelerate vaporizing, the oil stream is preferably subdivided into a plurality of smaller streams when it is mixed with the hot solid particles from the standpipes |4 (Figure l), |84 (Figure 2) and 232 (Figure).

Instead of or in addition to steam or the like used to strip the hot regenerated solid particles in standpipe I4 in Figure 1, hopper |82 in Figure 2 and withdrawal chamber 284 in Figure 3, a combustible gas such as a hydrocarbon gas may be introduced through lines 69, 2| 8 and 286 respectively, to reduced the oxygen concentration in the regenerated solid particles. v

As above described, the invention as shown in the different forms in the drawings contemplates using liquid oil at relatively low temperatures and without preheating the oil in a red coil or other heater and mixing this oil with hot regenerated solid particles to supply the heat necessary to vaporize and crack the oil. In order to have a sufficient quantity of solid particles to provide the necessary heat it is often necessary to substitute inert solid material for a portion of the catalyst particles. If only catalyst were used, the catalyst to oil ratio would be high, the time of reaction would be extremely short and it would be impossible to control the reaction in most cases. The mixture of solid particles andcatalyst particles during regeneration is heated to a temperature higher than the cracking temperature and these solid particles are directly mixed with the liquid oil to raise the oil to a cracking temperature.

When of a low coke-forming stock, the oil feed may be preheated by indirect heat exchange at a plurality of places in the process but a separate fired coil or heating furnace for vaporizing the oil is not required. The catalyst for cracking hydrocarbons may be any suitable one such as acid treated bentonite clay, synthetic gels containing silica and alumina or silica and magnesia. The inert solid material may be pumice, sand, kieselguhr, or any other similar material. catalyst particles and the solid heat carrier material are preferably of such size, shape and density that there is substantially no separation or segregation of the catalyst particles and heat carrier particles during the operation of the process. Preferably, the catalyst and heat care rier particles are of a size between about 200 and 400 standard meshor finer. In the catalytic cracking of oils, reduced crudes or gas oils may be used as the liquid feeds which are vaporized and raised to cracking temperature by the hot regenerated solid particles.

In some cases it may be desirable, however, to select the catalyst particles smaller or lighter than the inert particles. In the bottom drawoi type of reactor'the regenerator described in this application there would be a tendency for the smaller and lighter particles to remain longer in the vessels than the heavy, large particles which would be able to fall into the catalyst withdrawal spaces more readily. Thus, in catalytic cracking properly selected inert material Would normally contain no carbonaceous material after passing through the cracking zone.

Consequently, it is not necessary that it remain in the regeneration zone any longer than necessary for the absorption of its proportionate share of the heat of regeneration. This time is much shorter than would be necessary if carbonaceous material had to be removed therefrom. Con-f sequently, if the catalyst particles are either lighter or smaller than the inert particles it is sometimes possible to decrease the total pounds of solid held in the regenerator with a resultant saving in the regenerator cost. e

Conversely, if the inert particles are so selected that they are smaller or lighter than the catalyst particles, the catalyst residence time may be decreased and in some reactions this is desirable.

Where insuicient heat is produced during regeneration in the regeneration zones or vessels shown in the drawings, further heat may be supplied to the solid particles by firing the regeneration zones. Or, if the amount of heat produced during regeneration varies due to different amounts of carbonaceous deposits on the solid The a 10 particles from different oil stocks, the heat produced inthe regeneration -zone may be malntained substantially constant by ring the regeneration zone. For this ring suitable combustion material such as fuel oil or the like ilsl introduced into the bottom portion of the regeneration z one I2, for example in Figure 1, through line 300 below distribution plate 58 for admixture with the fouled solid particles introduced into the regeneration zone I2 through lines 54 and 56. In Figure 2 the combustible material is preferably introduced .into the regeneration zone 204 through line 302 and in Figure 3 through line 304 below distribution` plate 214.

In Figm'es 2 and 3 the 'levels |91, 205, 248 and 216 are similar to levels 2,2 and 62 described in connection with Figure 1.

In the form of the invention shown in Figure 1 of the drawings where it is desired to have about 45% conversion to gasoline of a reduced crude oil the cracking temperature is about 980 F. and the regeneration temperature is about 1150o F. In order to supply the heat of vaporization and cracking, the4 ratio of solid material to gas oil by weight is about 18 to 1. The catalyst is included in this solid to oil ratio and the amount of catalyst is about in the proportion of about 5 parts of catalyst to 1 part of oil by weight. The velocity of the vapors and gases in the reaction zone and regeneration zone is about 1.5 feet per second. Under these conditions about 5.4% carbon by weight 'is deposited on the solid particles and after regeneration about 1% carbonaceous material by weight remains on .the regenerated solid particles. Depending on the coke-forming characteristics of the stock, the oil feed may be preheated to temperatures from about '160 F. to 650 F. the higher temperatures giving lower carbonaceous deposits than the lower temperatures. With higher regeneration temperatures the amountof solid to oil used will be reduced.

In the reaction zone I0 Vthe fluidized mixture has a density of about 19.5 pounds per cubic foot and the densityof the suspension passing upwardly in lines 54 and 56 is about 2 pounds per cubic foot. The regenerator is maintained under a pressure of about 1 pound per square inch gauge and the reaction zone is maintained under a pressure of about 8 pounds per square inch gauge. 60 The reason for maintaining the reaction zone under a slight pressure is to provide suiicient pressure to overcome pressure drop through the lines and through the fractionating tower 40.

In the form of the invention shown in'Figure 2 the regeneration zone 204 is supported near ground level. Substantially the same conditions and results are obtained in this form ofthe invention as disclosed in connection with Figure 1 except that the velocity of the regenerating gas is about 3 feet per second.

In Figure 3 of the drawings the conditions of operation are-about the same as those given for Figure 1 with the exception that in the reaction zone 238 the velocity of the vapors and gases is 05 about 20 feet per second and the density of the mixture in the reaction zone 238 is about 7.7 pounds per cubic foot.

If desired or if necessary, suitable iluidizing gas may be introduced into the standpipes in Figures 1, 2 and 3 to maintain the solid particles in fiuidized condition'.

While the invention has been particularly described in connection with catalytic conversion or crackingof hydrocarbon oils, it is to be understood that it may also be used in other catalytic reactions such as oxidation, reduction, reforming of hydrocarbons, hydroforming of hydrocarbons, etc. My invention may also be used for carrying out conversions of hydrocarbons or other catalytic reactions generally where the reactants -are available in vapor or gas form and in these cases the regenerated hot solid particles are mixed with such vapors or gases to raise them to reaction temperature without using a vaporizing furnace.

While several forms of the invention have been shown and specific conditions and proportions given with respect to the particular forms shown, it is to be understood that these are by way of illustration only and various changes and modifications may be made without departing from the spirit of the invention.

This application is being filed as a division of my application Serial No. 424,872, led December 30, 1941, and now Patent Number 2,399,050, granted April 23, 1946.

I claim:

the reaction vessel for introducing hot regenerated solid particles in dense uidized condi- 1. An apparatus of the character described including a Iregeneration vessel and a reaction vessel arranged at about the same level, a shallow cup-shaped member arranged in the lower portion of the reaction vessel and maintained in spaced relation to the inner walls of the reaction vessel forming an annular passageaway between the outerwalls of said cup-shaped member and the inner walls of said reaction vessel into which the solid particles overow from said cup-shaped member, outlet means in the upper part of said reaction vessel for the withdrawal oi gaseous reaction products, a standpipe extending from within said shallow cup-shaped member upwardly throughthe top of the reaction vessel for introducing hot regenerated solid particles in dense uidized condition into said cup-Shaped member, conduit means for introducing liquid feed into the lower portion of said cup-shaped member, an outlet in the bottom of said reaction vessel for the withdrawal of solid particles from the lower portion of said annular passageway, a conduit for conducting withdrawn solid particles from said outlet into the lower portion of said regeneration vessel, means for introducing regenerating gas into said conduit in order to convey'the withdrawn solid particles into said regeneration vessel, a conduit arranged in the top of said regeneration vessel for removing the bulk of the hot regenerated solid particles and the regeneration gases overhead from said regeneration vessel, means for separating hot regenerated solid particles 'from regeneration gasesconnected to thedischarge end of said lastnamed conduit, said last-mentioned means be- -ing arranged at a higher level than said reaction vessel and being connected to the upper end of said standpipe whereby hot regenerated solid particles may be conveyed by gravity directly into said cup-shaped member.

2. An apparatus of the character described i cludlng a regeneration vessel and a reaction vessel, a shallow cup-shaped member arranged in the lower portion of said reaction vessel and maintained in spaced relation to the inner walls oi' said reaction vessel, forming an annular passageway between the outer Walls of said cupshaped member and the inner walls of said reaction vessel into which the solid particles leaving the cup-shaped member are discharged, an outlet in the top of said reaction vessel for the withdrawal of gaseous reaction products, a standpipe extending from within said cupshaped member upwardly through the top oi' tion into said cup-shaped member, conduit means for introducing liquid feed directly into the lower portion of said cup-shaped member for admixture with the solid particles and for forming a dense uidized mixture therewith, an inlet for the supply of stripping gas into said annular passageway, an outlet in the bottom of said reaction vessel for the discharge of spent solid particles, a conduit for conducting the spent solid particles from .the bottom of the reaction Vessel into the bottom portion of the regeneration 4vessel, means for introducing regenerating gas into said conduit for conveying the solid particles intosaid regeneration vessel, a conduit connected to the top of said regeneration vessel for removing the bulk of the hot regenerated particles and the regeneration gases overhead from said regeneration vessel, means for separating and cooling hot regenerated solid particles from the regeneration gases connected to the discharge end of said lastnamed conduit, said separating and cooling means being arranged at a higher level than said reaction vessel and being provided with fluidizing means for the cooled solids, said separating and cooling means being connected to the upper end of' said standpipewhereby hot regenerated solid particles may. be conveyed by gravity directly into said cup-shaped member.

3. A process for carrying out catalytic reactions which comprises introducing hot regenerated solid particles containing catalyst through a vertical standpipe directly into a dense fluidized mixture of solid particles and reactant in a reaction zone, introducing the stream of reactants in the liquid state into said reaction zone separately from said solid particles, controlling the amount of hot regenerated solid particles containing catalyst in the reaction zone to vaporize the feed and supply heat of reaction, maintaining the solid particles and reactant in a dense uidized condition in said reaction zone for a suicent time-to effect the desired extent of reaction, removing the reaction products containing only a minor amount of solid particles overhead from the vessel containing said reaction Zone, discharging spent solid particles from said reaction zone into the bottom portionparticles overhead from said regeneration zone,

separating hot regenerated particles from re-A generation gases and recycling the hot solidparticles by gravity into said reaction zone for admixture with additional liquid reactant feed.

4. A process for carrying catalytic cracking of hydrocarbons which comprises introducing hot regenerated catalyst particles through a vertical standpipe directly into a dense fluidized mixture of solid catalyst particles and hydrocarbon re-` actants in a conversion zone, introducing a stream of liquid hydrocarbons into said conversion zone separately from said catalyst particles, controlling the amount of hot regenerated cracking catalyst in the conversion zone to vaporize the hydrocarbons land supply the heat of cracking, maintaining the catalyst particlesy asoasov 13 and hydrocarbon 'vapors in a dense nuidized condition in said conversion zone for a suiilcient time to eiect the desired cracking, removing the vaporous reaction products containing only a minor amount of solid particles overhead from the vessel containing the conversion zone, discharging spent catalyst particles from said conversion zone into the bottom of the vessel, withdrawing spent catalyst particles from the bottom Y of said vessel in a fdense uidized condition separately from said vaporous reaction products. stripping the removed spent catalyst particles, mixing regenerating gas with the removed stripped catalyst particles and passing the resulting mixture into thev bottom'portion of a regeneration vessel, controlling velocity of the regenerating gas so as to remove the bulk of the hot regenerated catalyst particles and regeneration gases overhead vfrom said regeneration vessel, separating hot regenerated catalyst particles from the regeneration gases in a zone above said conversion zone and separate therefrom and passing the sepanated hot regenerated catalyst particles from said separating zone to said conversion zone for admixture with additional liquid hydrocarbons.

5. A process for carrying out catalytic reac-` tions which comprises vintroducing hot regenerated solid catalyst .particles through a vertical standpipe directly into a dense uidized mixture of catalyst or catalyst particles and reactants in a reaction zone, introducing a stream of reactants in the liquid state into said reaction.

zone separately from said solid catalyst particles, controlling the amount of hot regenerated solid catalyst particles in the reaction zone to vaporize the reactant feed and supply the heat of reaction, maintaining the solid catalyst particles and reactant in a dense fiuidized condition in said a regeneration zone arranged at about the same level as said reaction zone, controlling the velocity of the regenerating gas so as to remove' the bulk of the hot regenerated catalyst particles and regeneration gases overhead from said regeneration zone, separating hot regenerated solid catalyst particles from regeneration gases in a zone above said reaction zone and recycling the solid catalyst particles thus separated to said reaction zone las a downwardly moving column for admixture with additional liquid reactant feed.

^ HOMER Z. MARTIN.

REFERENCES CITED The following references are of record in the ille of this patent: y

UNITED STATES PATENTS Number Name Date 2,253,486 Belchetz Aug. 19 1941 2,337,684 Scheineman Dec. 28, 1943 2,340,878 Holt et al. Feb. 8, 1944 2,341,193' Scheineman Feb. 8, 1944 2,376,190 Roetheli et al May 15, 1945 2,399,050

Martin Apr. 23, 1946 

3. A PROCESS FOR CARRYING OUT CATALYTIC REACTIONS WHICH COMPRISES INTRODUCING HOT REGENERATED SOLID PARTICLES CONTAINING CATALYST THROUGH A VERTICAL STANDPIPE DIRECTLY INTO A DENSE FLUIDIZED MIXTURE OF SOLID PARTICLES AND REACTANT IN A REACTION ZONE, INTRODUCING THE STREAM OF REACTANTS IN THE LIQUID STATE INTO SAID REACTION ZONE SEPARATELY FROM SAID SOLID PARTICLES, CONTROLLING THE AMOUNT OF HOT REGENERATED SOLID PARTICLES CONTAINING CATALYST IN THE REACTION ZONE TO VAPORIZE THE FEED AND SUPPLY HEAT OF REACTION, MAINTAINING THE SOLID PARTICLES AND REACTANT IN A DENSE FLUIDIZED CONDITION IN SAID REACTION ZONE FOR A SUFFICIENT TIME TO EFFECT THE DESIRED EXTENT OF REACTION, REMOVING THE REACTION PRODUCTS CONTAINING ONLY A MINOR AMOUNT OF SOLID PARTICLES OVERHEAD FROM THE VESSEL CONTAINING SAID REACTION ZONE, DISCHARGING SPENT SOLID PARTICLES FROM SAID REACTION ZONE INTO THE BOTTOM PORTION OF SAID VESSEL, WITHDDRAWING SPENT SOLID PARTICLES FROM THE BOTTOM OF SAID VESSEL IN A DENSE FLUIDIZED CONDITION SEPARATELY FROM SAID REACTION PRODUCTS, MIXING REGENERATING GAS WITH THE REMOVED PARTICLES AND PASSING THE RESULTING MIXTURE INTO THE BOTTOM PORTION OF A REGENERATION ZONE, CONTROLLING THE VELOCITY OF THE REGENERATING GAS SO AS TO REMOVE THE BULK OF THE HOT REGENERATED SOLID PARTICLES OVERHEAD FROM SAID REGENERATION ZONE, SEPARATING HOT REGENERATED PARTICLES FROM REGENERATION GASES AND RECYCLING THE HOT SOLID PARTICLES BY GRAVITY INTO SAID REACTION ZONE FOR ADMIXTURE WITH ADDITIONAL LIQUID REACTANT FEED. 